Bis(diethylamino)pentafluorophenylphosphane as Valuable Precursor for the Design of Tetrafluorophenylphosphanes, Tetrafluorophenylphosphinic and -phosphonic Acids

Article abstract of DOI:10.1002/ejic.201701402

Facile replacement of the p-fluorine atom in bis(diethylamino)pentafluorophenylphosphane [(Et₂N)₂PC₆F₅] by organolithium derivatives LiR (R = CH₃, n-Bu, Ph), lithium alkoxides (R = OMe, OEt) and amides (NMe₂, NEt₂) is described. The obtained phosphanes p-R-C₆F₄-P(NEt₂)₂ are fully characterized. Their acid-catalyzed hydrolysis affords the corresponding phosphinic acids p-R-C₆F₄-P(O)(H)OH, which are smoothly oxidized by treatment with a mixture of DMSO/I₂ to phosphonic acids p-R-C₆F₄-P(O)(OH)₂.

Full text of DOI:10.1002/ejic.201701402

DOI: 10.1002/ejic.201701402
Full Paper
Fluorinated Phosphorus Compounds
Bis(diethylamino)pentafluorophenylphosphane as Valuable
Precursor for the Design of Tetrafluorophenylphosphanes,
Tetrafluorophenylphosphinic and -phosphonic Acids
Christian Alter,[a] Beate Neumann,[a] Hans-Georg Stammler,[a] and Berthold Hoge*[a]
Abstract: Facile replacement of the p-fluorine atom in bis(di- Their acid-catalyzed hydrolysis affords the corresponding phos-
ethylamino)pentafluorophenylphosphane [(Et2N)2PC6F5] by or-
ganolithium derivatives LiR (R = CH3, n-Bu, Ph), lithium alkox-
ides (R = OMe, OEt) and amides (NMe2, NEt2) is described. The
obtained phosphanes p-R-C6F4-P(NEt2)2 are fully characterized.
phinic acids p-R-C6F4-P(O)(H)OH, which are smoothly oxidized
by treatment with a mixture of DMSO/I2 to phosphonic acids
p-R-C6F4-P(O)(OH)2.
Introduction
In recent years considerable interest has been spent on aryl-
phosphinic and arylphosphonic acids. This is mainly due to the
widespread applications of such species for the fabrication of
functional polymers and membranes,[1] or for surface modifica-
tors and self-assembling materials.[2] Moreover they function as
important ligands[3] and ingredients for rare earth metal extrac-
tion,[4] as well as for the manufacturing of flame retardants,[5]
agrochemicals[6] and pharmaceuticals.[7]
In this context fluorinated derivatives are of particular impor-
tance as organofluorine functionalities significantly influence
the properties of drugs or agrochemicals.[8] Polymers bearing
fluorinated arylphosphonic acids as substituents are promising
Scheme 1. Syntheses of fluorinated arylphosphinic acids starting from pro-
tected chlorophosphanes.
phenylphosphinic acids. Derivatives of this type, as evidenced
by the literature, are limited to pentafluorophenylphos-
phinic acid and 2,3,5,6-tetrafluorophenylphosphinic acid
(Scheme 1).[11,13]
Highly fluorinated arylphosphonic acids are generally acces-
as materials of high stability for proton conducting membranes sible by two classical synthetic routes, the Michaelis–Arbuzov
in fuel cells.[9] In surface modification studies, fluorinated phos- and the Michaelis–Becker reaction. Both protocols yield dialkyl-
phonic acids exhibit pronounced bidentate binding affinities.[10] phosphonates, which by subsequent dealkylation yield the cor-
responding phosphonic acid.
Despite these challenging perspectives and the vast scope
of applications, protocols for the synthesis of functionalized,
The Michaelis–Arbuzov reaction of trialkylphosphites with
highly fluorinated arylphosphinic- and phosphonic acids are fluorinated aromatics requires very harsh conditions. This proc-
only rare.
Fluorinated arylphosphinic acids are generally accessible by
the reaction of lithium aryls with phosphorus(III) halides or pro-
tected derivatives thereof, for example, ClP(NEt2)2. Hydrolysis of
ess is not selective and distillation is necessary to purify the
products which are isolated in only low yields (25–30 %)
(Scheme 2).[14]
The Michaelis–Becker reaction, utilizing sodium diethylphos-
bis(amino)arylphosphanes leads to fluoroarylphosphinic acids phites, operates under more moderate conditions (THF, 70 °C)
(Scheme 1).[11] In addition to this multistep synthesis, fluoroaryl- and yields the arylphosphonates in low to good yields after
phosphinic acids are accessible via several transition metal cata- distillation (10–65 %) (Scheme 3).[15]
lyzed procedures.[12]
Here we report on the functionalization of bis(diethyl-
To the best of our knowledge no widely applicable protocols amino)pentafluorophenylphosphane simply by nucleophilic
are known for the synthesis of para substituted tetrafluoro- substitution of the para fluorine atom with lithium nucleophiles
LiR. This discovery opens up a new avenue for the generation
of para substituted tetrafluoroarylphosphinic and phosphonic
acids. The starting material, C6F5P(NEt2)2, is readily available
from the reaction of C6F5Li with ClP(NEt2)2. We improved this
procedure essentially by the use of C6F5MgBr as the penta-
fluorophenyl transfer reagent, thus avoiding the labile C6F5Li,
which tends to decompose violently at temperatures above
[a] Universität Bielefeld, Fakultät für Chemie,
Centrum für Molekulare Materialien,
Universitätsstraße 25, 33615 Bielefeld, Germany
E-mail: b.hoge@uni-bielefeld.de
https://www.uni-bielefeld.de/chemie/acii/hoge/
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejic.201701402.
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Scheme 2. Michaelis–Arbuzov reaction of triethylphosphite with fluorinated benzene and pyridine derivatives.
nucleophilic substitution with Grignard reagents failed. The re-
sults of the substitution reactions are presented in Table 1.
Table 1. Isolated yields, 31P and 19F NMR chemical shifts of phosphanes 1–
8.[a]
R
19F (ortho)
[ppm]
19F (meta)
[ppm]
31P
[ppm]
Yield
[%]
F (1)
–136.4
–138.5
–138.3
–138.0
–138.2
–138.8
–138.9
–137.2
–162.3
–144.6
–145.8
–158.2
–157.6
–151.9
–149.7
–144.9
78.6
79.2
79.4
78.9
78.9
79.3
79.3
79.5
–
Me (2)
nBu (3)
OMe (4)
OEt (5)
NMe2 (6)
NEt2 (7)
Ph (8)
81
67
66
58
70
75
89
Scheme 3. Michaelis–Becker reaction of sodium diethylphosphites with fluor-
inated benzene derivatives.
–50 °C while C6F5MgBr is stable at room temperature in ethereal
solution.[11] Thus C6F5P(NEt2)2 is now easily accessible on a
multi-gram scale from cheap, commercially available precursors
(PCl3, HNEt2, C6F5Br, Mg).[11,16]
[a] Solvent: CDCl3.
Lithium dialkylamides react readily with C6F5P(NEt2)2 at 0 °C
within minutes. The reaction of alkyllithium species or LiPh
takes two hours to complete, and use of LiOEt requires heating
of the THF solution at 66 °C for 19 hours. All nucleophiles, ex-
cept LiOMe, react selectively by substitution of the para fluorine
atom, leaving C6F5P(NEt2)2 as the only impurity after separation
from LiF. As with LiOMe, no reaction is observed in THF at room
temperature or 66 °C. The expected substitution, however, pro-
ceeds in boiling methanol as a solvent. Prolonged reaction
times lead to the cleavage of the carbon phosphorus bond and
should be avoided. All newly prepared phosphanes were puri-
fied by vacuum distillation and fully characterized by means of
NMR spectroscopy, IR spectroscopy and mass spectrometry. As
presented in Table 1 the nature of the substituent has a dra-
matic influence on the 19F NMR chemical shift of the adjacent
m-fluorine atoms ranging from –162.3 ppm in phosphane 1 to
–144.6 ppm in phosphane 2.
Results and Discussion
The starting material C6F5P(NEt2)2 (1) was prepared by the
straightforward and cost-efficient reaction of in situ generated
C6F5MgBr with ClP(NEt2)2 (Scheme 4).
Scheme 4. Synthesis of bis(diethylamino)pentafluorophenylphosphane 1.
Synthesis of Tetrafluorophenylphosphane Derivatives
Aminophosphanes 1–8 are moisture sensitive and contact
with water leads to hydrolysis.
Bis(diethylamino)pentafluorophenylphosphane 1 is functional-
ized by nucleophilic replacement of the para fluorine atom at
the ring with organolithium compounds, lithium dialkylamides
and lithium alcoholates (Scheme 5). Obviously, the elimination
of LiF serves as a driving force of the reaction. In our studies
Synthesis of Tetrafluorophenylphosphinic Acids
The hydrolysis of the bis(diethylamino)phosphanes 1–8 with
aqueous HCl to produce phosphinic acids 9–16 was completed
within hours. After phase separation, extraction with diethyl
ether and drying in vacuo the analytically pure acids were ob-
tained in excellent yields (80–97 %) (Scheme 6). Phosphinic acid
16, resulting from hydrolysis of phosphane 8, is only poorly
soluble in Et2O and water and precipitates during the hydroly-
sis. The 31P NMR resonances of the phosphinic acids 9–16 are
observed as doublets in the range of δ = –1.0 to 10.4 ppm with
1
a JPH coupling constant of 600 to 635 Hz, and are thus high
field shifted by ca. 70 ppm in comparison to the corresponding
Scheme 5. Nucleophilic substitution of bis(diethylamino)pentafluorophenyl-
phosphane 1.
aminophosphanes 1–8 (Table 2).
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phosphinic acid.[11b] The O1–O2′ distance amounts to 243.9(2)
pm.
Synthesis of Tetrafluorophenylphosphonic Acids
Mild oxidation of the phosphinic acids 9–16 to the correspond-
ing phosphonic acids 17–24[18] was performed by an equimolar
amount of DMSO and catalytic quantities of iodine in methyl-
tert-butyl ether (MTBE) (Scheme 7). After evaporation of the sol-
vent and drying in vacuo analytically pure phosphonic acids are
obtained in 78–99 % yield. The oxidation of phosphinic acid 16
to 24 in MTBE is very sluggish and takes more than seven days.
Changing the solvent to toluene accelerates this process signifi-
cantly so that completion was reached after 24 hours (Table 3).
All of the presented tetrafluorophenylphosphonic acids repre-
sent hitherto unknown compounds. Alkyl esters of 20 are de-
scribed in the literature and accessible by the Michaelis–
Arbuzov reaction in 24 % yield.[15] The isolated compounds are
not hygroscopic and well soluble in acetonitrile, methanol and
DMSO. All compounds except phosphonic acid 24 are also solu-
ble in water.
Scheme 6. Hydrolysis of bis(diethylamino)phosphanes 1–8 with hydrochloric
acid.
Table 2. Isolated yields, 31P and 19F NMR chemical shifts of the obtained
phosphinic acids 9–16.[a]
R
19F (ortho)
[ppm]
19F (meta)
[ppm]
31P
[ppm]
Yield
[%]
F (9)
–135.3
–138.1
–137.7
–137.3
–137.4
–138.3
–138.4
–138.5
–158.9
–141.4
–142.7
–156.3
–155.7
–151.6
–149.8
–142.8
6.9
80
81
92
97
93
83
96
80
1J(P,H) = 635 Hz
9.5
Me (10)
nBu (11)
OMe (12)
OEt (13)
NMe2 (14)
NEt2 (15)
Ph (16)
1J(P,H) = 630 Hz
8.4
1J(P,H) = 627 Hz
9.1
1J(P,H) = 627 Hz
8.2
1J(P,H) = 627 Hz
10.2
1J(P,H) = 622 Hz
10.4
1J(P,H) = 624 Hz
–1.0
1J(P,H) = 600 Hz
[a] Solvent: CDCl3,16: [D6]DMSO.
Scheme 7. Oxidation of the phosphinic acids 9–16 to the phosphonic acids
17–24.
Compounds 9–16 are air stable and, with exception of 16,
well soluble in acetonitrile, chloroform and dichloromethane.
Single crystals of phosphinic acid 12 are grown from a dichloro-
methane solution and subjected to an X-ray diffraction analysis
(Figure 1). The phosphinic acid crystallizes in the orthorhombic
space group P212121. The crystal structure reveals a molecular
unit with one short PO bond [d(P1–O1) = 149.5(1) pm] and
one long PO bond [d(P1–O2) = 152.9(1) pm]. Intermolecular
hydrogen bonding between O1 and O2′ constitutes a chain
structure, similar to the one observed for pentafluorophenyl-
Table 3. Isolated yields, 31P and 19F NMR chemical shifts of phosphonic acids
17–24 in [D6]DMSO.
R
19F (ortho)
[ppm]
19F (meta)
[ppm]
31P
[ppm]
Yield
[%]
F (17)
–133.0
–134.8
–133.7
–134.5
–134.4
–135.3
–135.1
–133.5
–161.6
–143.2
–143.9
–157.7
–157.0
–152.1
–150.3
–143.6
–2.0
–1.2
–0.7
–1.1
–1.0
–0.0
–0.3
–1.5
95
89
98
99
96
98
94
78
Me (18)
nBu (19)
OMe (20)
OEt (21)
NMe2 (22)
NEt2 (23)
Ph (24)
Single crystals of phosphonic acid 21 were grown from tolu-
ene at –80 °C and were subjected to an X-ray diffraction study
(Figure 2). The molecule displays the geometry of a distorted
tetrahedron about the phosphorus atom [O3–P1–C1
=
108.3(1)°; O1–P1–O3 = 113.5(1)°; O1–P1–O2 = 114.5(1)°; O1–P1–
C1 = 109.6(1)°]. For the P1–C1 distance 179.9(2) pm and for the
C4–O4 distance 134.0(2) pm were measured.
Single crystals of phosphonic acid 24 were obtained from a
methanol solution by slow evaporation of the solvent (Figure 3).
An X-ray structural analysis exhibits two crystallographically in-
dependent molecules per asymmetric unit and one equivalent
methanol per molecule. The biphenyl substituent is twisted at
the phosphorus atom with P–C bond lengths of 180.7(1) pm
Figure 1. Molecular structure of p-(CH3O)C6F4P(O)(OH)H (12) in the crystal
(thermal ellipsoids are set to 50 % probability).
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whilst O2 and O3 are bridged to the oxygen atoms O1# and
O1′ of the adjacent molecules. X-ray studies on crystals of phos-
phonic acid 19 reveal a similar hydrogen bonding network (Fig-
ure 5).
Figure 2. Molecular structure of p-(EtO)C6F4P(O)(OH)2 (21) in the crystal (ther-
mal ellipsoids are set to 50 % probability, aliphatic hydrogen atoms omitted).
resp. 180.5(1) pm and encloses an interplanar angle of about
53° with the tetrafluorophenylene unit. The phosphonic acid is
involved in a complex system of hydrogen bridging in the solid
state under participation of methanol.
Figure 3. Molecular structure of p-(C6H5)C6F4P(O)(OH)2 (24) in the crystal
(thermal ellipsoids are set to 50 % probability).
Figure 5. Molecular structure of p-(nBu)C6F4P(O)(OH)2 (19) in the crystal (ther-
mal ellipsoids are set to 50 % probability, aliphatic hydrogen atoms omitted).
Single crystals of 17 were grown from toluene, and its crystal
structure was ascertained by X-ray diffraction. The compound
crystallizes in the monoclinic space group P21/n (Figure 4). Simi-
lar to phenylphosphonic acid, pentafluorophenylphosphonic
acid exhibits a network of hydrogen bridges in the solid
state.[17] The tetra coordinated phosphorus atom unveils one
short {d[P1–O1 = 149.9(1) pm]} and two long [d(P1–O2) =
154.2(1) pm, d(P1–O3) = 154.6(1) pm] PO bonds. O1 is bridged
by two hydrogen atoms (H2′, H3#) from two adjacent molecules
The X-ray structure of phosphonic acid 23 reveals two differ-
ent molecules in the asymmetric unit (Figure 6). The nitrogen
N1 is tetrahedrally coordinated by two ethyl groups, one aryl
moiety and hydrogen atom H1 [C4–N1–C7 = 112.6(1)°; C4–N1–
C9 = 113.1(1)°; C7–N1–C9 = 110.0(1)°]. Thereby, protons H2 and
H3 have an atomic occupancy of 50 % each. In contrast to this
zwitterionic ammonium hydrogenphosphonate structure, N2 of
the second molecule remained nonprotonated [C14–N2–C17 =
114.8(1)°; C14–N2–C19 = 119.5(1)°; C19–N2–C17 = 116.0(1)°].
Figure 4. Molecular structure of pentafluorophenylphosphonic acid (17) in
Figure 6. Molecular structure of p-(Et2N)C6F4P(O)(OH)2 (23) in the crystal (ther-
the crystal (thermal ellipsoids are set to 50 % probability).
mal ellipsoids are set to 50 % probability, aliphatic hydrogen atoms omitted).
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p-(CH3)C6F4P(NEt2)2 (2): A sample of bis(diethylamino)pentafluoro-
phenylphosphane (5.00 g; 14.6 mmol) was dissolved in THF (50 mL)
Conclusions
We reported a straightforward synthesis for novel tetrafluoro-
phenylphosphanes, phosphinic acids and phosphonic acids.
and methyllithium (9.1 mL; 1.6
M in Et2O, 14.6 mmol) was added
dropwise at –80 °C. After stirring for two hours the solvent was
The starting material C6F5P(NEt2)2 was prepared by the reaction evaporated and the crude product condensed off in dynamic vacuo
at 350 °C. Distillation in dynamic vacuo yielded 4.00 g of the prod-
of C6F5MgBr with ClP(NEt2)2. Nucleophilic substitution of the
para fluorine atom was achieved with seven different lithium
nucleophiles (MeLi, nBuLi, MeOLi, EtOLi, Me2NLi, Et2NLi and
PhLi) to furnish novel functionalized tetrafluorophenylphos-
phanes 1–8. The corresponding phosphinic acids 9–16 are eas-
ily accessible via hydrolysis with hydrochloric acid. Subsequent
oxidation affords the corresponding phosphonic acids 17–24.
1
uct (b.p. = 65.0 °C; 11.8 mmol; 81 %) as a colorless liquid. H NMR
3
(CDCl3, r.t.): δ = 1.06 [t, J(H,H) = 7 Hz, 12 H, CH3], 2.24 [pseudo q,
3
3
J(H,F/P) = 2 Hz, 3 H, CH3], 3.07 [dq, J(P,H) = 10, J(H,H) = 7 Hz, 8 H,
CH2] ppm. 13C{1H} NMR (CDCl3, r.t.): δ = 7.7 (m, CH3), 14.9 [d,
3J(P,C) = 3 Hz, CH3], 44.3 [dt, J(P,C) = 19, J(F,C) = 1 Hz, CH2] ppm.
2
5
13C{19F} NMR (CDCl3, r.t.): δ = 7.7 [qd, J(C,H) = 132, J(P,C) = 1 Hz,
CH3], 115.3 [qd, 2J(C,H) = 6, 4J(P,C) = 2 Hz, C-CH3], 119.0 [d, 1J(P,C) =
46 Hz, C-P], 145.1 [dq, 3J(P,C) = 4, 3J(C,H) = 2 Hz, CF], 145.4 [dm,
2J(P,C) = 12 Hz, CF] ppm. 19F NMR (CDCl3, r.t.): δ = –138.5 (m, 2 F,
CF-ortho), –144.6 (m, 2 F, CF-meta) ppm. 31P NMR (CDCl3, r.t.): δ =
1
5
Experimental Section
79.2 (m, 1 P, P) ppm. IR (ATR): ν = 2968 (w), 2931 (w), 2864 (w), 1580
[16]
˜
The starting material ClP(NEt2)2
was synthesized as described in
(w), 1441 (s), 1375 (m), 1360 (shoulder, w), 1292 (m), 1253 (m), 1198
(m), 1115 (m), 1098 (w), 1060 (m), 1027 (m), 1014 (s), 974 (w), 927
(m), 904 (s), 787 (m), 722 (w), 668 (m), 642 (w), 605 (w), 580 (w), 502
(w), 478 (w), 440 (w), 418 (w) cm–1. MS (EI, 70 eV, pos.): m/z (%) =
338.0 (17) [M]·+, 266.9 (13) [C11H14F4NP]·+, 265.9 (100) [C11H13F4NP]+,
194.9 (17) [C7H4F4P]+, 103.9 (10) [C4H11NP]+. HRMS (ESI): calcd. for
C15H23F4N2PH+ 339.1613, found 339.1621.
the literature. All other chemicals were obtained from commercial
sources and used without further purification. Standard high-vac-
uum techniques were employed throughout all experiments. Non-
volatile compounds were handled in a dry N2 atmosphere using
Schlenk techniques. The crystal data were collected on a Rigaku
Supernova diffractometer at 100 K using Mo-Kα or Cu-Kα radiation.
All non-hydrogen atoms were refined anisotropically, all donor
hydrogen atoms were refined isotropically. Details of the X-ray in-
vestigation are given in the Supporting Information. IR spectra were
recorded with a Bruker Alpha FTIR spectrometer (Bruker Daltonik
GmbH, Bremen, Germany) equipped with an ATR unit with a dia-
mond crystal for liquids and solids. The NMR spectra were recorded
on a Bruker Model Avance III 300 spectrometer (31P 121.5 MHz; 19F
p-(C4H9)C6F4P(NEt2)2 (3): A sample of bis(diethylamino)penta-
fluorophenylphosphane (8.54 g; 25.0 mmol) was dissolved in THF
(50 mL) and n-butyllithium (16.25 mL; 1.6
M in n-hexane, 26.0 mmol)
was added dropwise at 0 °C. After stirring for two hours the solvent
was evaporated and the crude product condensed off in dynamic
vacuo at 350 °C. Distillation in dynamic vacuo yielded 6.43 g of the
product (b.p. = 84.7 °C; 16.4 mmol; 67 %) as a colorless liquid. 1H
NMR (CDCl3, r.t.): δ = 0.96 [t, 3J(H,H) = 7 Hz, 3 H, CH3], 1.09 [t,
3J(H,H) = 7 Hz, 12 H, CH3], 1.39 (m, 2 H, CH2), 1.60 (m, 2 H, CH2),
1
282.4 MHz; 13C 75.5 MHz; H 300.1 MHz) with positive shifts being
downfield from the external standards [TMS (13C;1H), CCl3F (19F);
85 % H3PO4 (31P)]. ESI mass spectra were recorded using an Esquire
3000 ion-trap mass spectrometer (Bruker Daltonik GmbH, Bremen,
Germany) equipped with a standard ESI/APCI source. EI mass spec-
tra were recorded using an Autospec Xmagnetic sector mass spec-
trometer with EBE geometry (Vacuum Generators, Manchester, UK)
equipped with a standard EI or CI source. Melting points were meas-
ured on a Mettler Toledo Mp70 Melting Point System.
3
3
2.72 (m, 2 H, CH2), 3.10 [dq, J(P,H) = 10, J(H,H) = 7 Hz, 8 H, CH2]
ppm. 13C{1H} NMR (CDCl3, r.t.): δ = 13.7 (s, CH3), 14.8 [d, 3J(P,C) =
3 Hz, CH3], 22.3 (s, CH2), 22.6 (m, CH2), 31.4 (s, CH2), 44.1 [dt, 2J(P,C) =
19, 5J(F,C) = 1 Hz, CH2] ppm. 13C{19F} NMR (CDCl3, r.t.): δ = 119.0 [d,
1J(P,C) = 46 Hz, C-P], 120.0 (m, C-CH2), 144.8 [td, 3J(C,H) = 5, 3J(P,C) =
2 Hz, CF], 145.3 [d, 2J(P,C) = 12 Hz, CF] ppm. 19F NMR (CDCl3, r.t.):
δ = –138.3 (m, 2 F, CF-ortho), –145.8 (m, 2 F, CF-meta) ppm. 31P
CCDC 1586050 [for p-(CH3O)C6F4P(O)(OH)H], 1586051 [for
C6F5P(O)(OH)2], 1586052 [for p-(nBu)C6F4P(O)(OH)2], 1586053 [for p-
NMR (CDCl3, r.t.): δ = 79.4 (m, 1 P, P) ppm. IR (ATR): ν = 2965 (w),
˜
2931 (w), 2864 (w), 1512 (w), 1441 (m), 1401 (w), 1375 (m), 1293
(w), 1247 (m), 1198 (m), 1183 (m), 1123 (w), 1095 (w), 1077 (w),
1059 (w), 1014 (s), 972 (m), 963 (m), 927 (m), 909 (m), 787 (m), 754
(w), 737 (w), 712 (w), 669 (m), 639 (m), 604 (w), 579 (w), 503 (w),
419 (w) cm–1. MS (EI, 70 eV, pos.): m/z (%) = 380.1 (20) [M]·+, 308.1
(100) [C14H19F4NP]+, 270.0 (18), 175.1 (10) [C8H20N2P]+, 104 (19)
[C4H11NP]+, 72.1 (36) [C4H10N]+. HRMS: calcd. for C18H29F4N2P·+
380.19990, found 380.20177.
(C2H5O)C6F4P(O)(OH)2],
1586054
[for
(Et2N)C6F4P(O)(OH)2·
p-(Et2NH)C6F4P(O)2(OH)·3H2O], and 1586055 [for p-(C6H5)C6F4P(O)-
(OH)2·MeOH] contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre.
Synthesis of Bis(diethylamino)phosphanes
C6F5P(NEt2)2 (1): A sample of magnesium turnings (8.00 g;
330 mmol) was suspended in diethyl ether (400 mL). The suspen- p-(CH3O)C6F4P(NEt2)2 (4): A sample of n-butyllithium (27.4 mL;
sion was stirred and C6F5Br (43.0 g; 175 mmol), dissolved in diethyl 1.6
M
in n-hexane, 24.4 mmol) was added to dry methanol (100 mL)
ether (100 mL), was slowly added and the resulting suspension re-
and stirred for 10 min at room temperature. A sample of bis(diethyl-
fluxed for two hours. After the solution was cooled to room temper- amino)pentafluorophenylphosphane (10.0 g; 29.2 mmol) was added
ature ClP(NEt2)2 (36.8 g; 175 mmol), dissolved in diethyl ether and the reaction mixture was refluxed for 48 h. The solvent was
(200 mL), was added dropwise at 0 °C. The solution was stirred at evaporated and the crude product dissolved in n-pentane (50 mL)
room temperature for 18 h. After filtration and removal of the sol-
vent the raw product was distilled in dynamic vacuo to yield 46.5 g
of C6F5P(NEt2)2 (b.p. = 78.0 °C; 136 mmol; 80 %) as a colorless liquid.
1H NMR (CDCl3, r.t.): δ = 1.06 [t, 3J(H,H) = 7 Hz, 12 H, CH3], 3.06 [dq,
and filtered. Separation from the solvent and distillation in dynamic
vacuo yielded 6.49 g of the product (b.p. = 81.7 °C; 19.3 mmol;
66 %) as a colorless liquid. 1H NMR (CDCl3, r.t.): δ = 1.06 [t, 3J(H,H) =
3
3
10 Hz, 12 H, CH3], 3.06 [dq, J(P,H) = 10, J(H,H) = 7 Hz, 8 H, NCH2],
3J(P,H) = 10, 3J(H,H) = 7 Hz, 8 H, CH2] ppm. 19F NMR (CDCl3, r.t.): δ = 4.06 [t, 5J(F,H) = 1 Hz, 3 H, OCH3] ppm. 13C{1H} NMR (CDCl3, r.t.): δ =
–136.4 [m, J(P,F) = 26, J(F,F) = 13 Hz, 2 F, CF-ortho], –155.5 (m, 1 F,
CF-para), –162.3 (m, 2 F, CF-meta) ppm. 31P NMR (CDCl3, r.t.): δ =
78.6 (m, 1 P, P) ppm.
14.9 [d, 3J(P,C) = 3 Hz, CH3], 44.2 [dt, 2J(P,C) = 19, 5J(F,C) = 1 Hz,
3
7
NCH2], 62.0 [td, 4J(F,C) = 4, J(P,C) = 2 Hz, OCH3] ppm. 13C{19F} NMR
1
4
(CDCl3, r.t.): δ = 114.7 [d, J(P,C) = 47 Hz, C-P], 137.7 [dq, J(P,C) = 4,
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3
2
3J(C,H) = 2 Hz, C-O], 140.8 [d, J(P,C) = 2 Hz, CF], 146.1 [d, J(P,C) =
12 Hz, CF] ppm. 19F NMR (CDCl3, r.t.): δ = –138.0 (m, 2 F, CF-ortho),
–158.2 (m, 2 F, CF-meta) ppm. 31P{1H} NMR (CDCl3, r.t.): δ = 78.9 (m,
H]+, 295.1 (32). HRMS: calcd. for C16H26F4N3PH+ 368.18732, found
368.1879.
p-[(C2H5)2N]C6F4P(NEt2)2 (7): A sample of n-butyllithium (15.3 mL;
1 P, P) ppm. IR (ATR): ν = 2968 (w), 2932 (w), 2864 (w), 1635 (w),
˜
1.6
M in n-hexane, 24.4 mmol) was dissolved in THF (50 mL). The
1496 (m), 1448 (s), 1375 (m), 1360 (m), 1292 (w), 1269 (w), 1197 (m),
1182 (s), 1100 (s), 1058 (w), 1014 (s), 975 (s), 926 (s), 911 (m), 787
(m), 733 (w), 670 (m), 638 (m), 576 (w), 505 (w), 477 (w), 447 (w),
422 (w) cm–1. MS (EI, 70 eV, pos.): m/z (%) = 354.2 (23) [M]·+, 283.1
(13) [C11H14F4NOP]·+, 282.1 (100) [C11H13F4NOP]+, 211.0 (67)
[C7H4F4OP]+. HRMS: calcd. for C15H23F4N2OP·+ 354.14787, found
354.14876.
solution was degassed at –80 °C and diethylamine (24.4 mmol) was
condensed onto the solution. The reaction mixture was stirred for
30 min and allowed to reach 0 °C. At 0 °C bis(diethylamino)penta-
fluorophenylphosphane (8.00 g; 23.4 mmol) was added dropwise.
The reaction mixture was stirred for 20 min at room temperature.
The solvent was evaporated and the crude product condensed off
in dynamic vacuo at 350 °C. Distillation in dynamic vacuo yielded
6.90 g of the product (b.p. = 73.0 °C; 17.5 mmol; 75 %) as a colorless
liquid. 1H NMR (CDCl3, r.t.): δ = 1.07 [t, 3J(H,H) = 7 Hz, 18 H, CH3],
p-(C2H5O)C6F4P(NEt2)2 (5): A sample of ethanol (1.22 g; 26.6 mmol)
was dissolved in THF (50 mL) and n-butyllithium (16.6 mL; 1.6
M in
3
3
3
3.08 [dq, J(P,H) = 10, J(H,H) = 7 Hz, 8 H, NCH2], 3.21 [qt, J(H,H) =
7, 5J(F,H) = 1 Hz, 2 H, C-NCH2] ppm. 13C{1H} NMR (CDCl3, r.t.): δ =
13.3 (s, CH3), 14.8 [d, 3J(P,C) = 3 Hz, CH3], 44.1 [dt, 2J(P,C) = 19,
n-hexane, 26.6 mmol) was added dropwise at 0 °C. After stirring for
30 min at room temperature bis(diethylamino)pentafluorophenyl-
phosphane (7.00 g; 20.5 mmol) was added. The reaction mixture
was refluxed for 19 h. The solvent was evaporated and the crude
product condensed off in dynamic vacuo at 350 °C. Destillation in
dynamic vacuo yielded 4.38 g of the product (b.p. = 66.9 °C;
11.9 mmol; 58 %) as a colorless liquid. 1H NMR (CDCl3, r.t.): δ = 1.05
[t, 3J(H,H) = 10 Hz, 12 H, CH3], 1.40 [t, 3J(H,H) = 7 Hz, 3 H, CH3], 3.06
[dq, 3J(P,H) = 10, 3J(H,H) = 7 Hz, 8 H, NCH2], 4.27 [qt, 3J(H,H) = 7,
5J(F,H) = 1 Hz, 2 H, OCH2] ppm. 13C{1H} NMR (CDCl3, r.t.): δ = 14.8
[d, J(P,C) = 3 Hz, CH3], 15.4 (s, CH3), 44.1 [dt, J(P,C) = 19, J(F,C) =
1 Hz, NCH2], 70.6 [tm, 4J(F,C) = 3 Hz, OCH2] ppm. 13C{19F} NMR
(CDCl3, r.t.): δ = 114.6 [d, 1J(P,C) = 47 Hz, C-P], 136.5 [pseudo q,
3J(H,C)/4J(P,C) = 3 Hz, C-O], 141.0 [d, 3J(P,C) = 2 Hz, CF], 145.9 [d,
2J(P,C) = 12 Hz, CF] ppm. 19F NMR (CDCl3, r.t.): δ = –138.2 (m, 2 F,
CF-ortho), –157.6 (m, 2 F, CF-meta) ppm. 31P{1H} NMR (CDCl3, r.t.):
5J(F,C) = 1 Hz, NCH2], 47.1 [tm, J(F,C) = 3 Hz, CNCH2] ppm. 13C{19F}
4
1
NMR (CDCl3, r.t.): δ = 114.6 [d, J(P,C) = 44 Hz, C-P], 127.9 (m, C-N),
3
2
144.0 [d, J(P,C) = 2 Hz, CF], 146.0 [d, J(P,C) = 12 Hz, CF] ppm. 19F
NMR (CDCl3, r.t.): δ = –138.9 (m, 2 F, CF-ortho), –149.7 (m, 2 F, CF-
meta) ppm. 31P{1H} NMR (CDCl3, r.t.): δ = 79.3 (m, 1 P, P) ppm. IR
(ATR): ν = 2968 (m), 2932 (w), 2867 (w), 1629 (w), 1488 (w), 1439
˜
(s), 1375 (m), 1361 (m), 1344 (w), 1293 (w), 1264 (w), 1196 (s), 1183
(s), 1072 (m), 1014 (s), 963 (s), 925 (s), 853 (w), 787 (m), 756 (w), 670
(m), 638 (w), 552 (w), 499 (w), 420 (w) cm–1. MS (EI, 70 eV, pos.):
m/z (%) = 395.1 (32) [M]·+, 324.1 (14) [C14H21F4N2P]·+, 323.0 (78)
[C14H20F4N2P]+, 237.0 (23), 208.0 (10). HRMS: calcd. for
C18H30F4N3P·+ 395.21080, found 395.21203.
3
2
5
p-(C6H5)C6F4P(NEt2)2 (8): A sample of bromobenzene (4.45 g;
δ = 78.9 (m, 1 P, P) ppm. IR (ATR): ν = 2969 (w), 2932 (w), 2866 (w), 28.3 mmol) was dissolved in THF (50 mL) and n-butyllithium
˜
1634 (w), 1493 (m), 1477 (s), 1375 (m), 1360 (m), 1292 (w), 1264 (w), (16.25 mL; 1.6
M in n-hexane, 26.0 mmol) was added dropwise at
1198 (m), 1183 (m), 1094 (s), 1055 (w), 1014 (s), 968 (s), 927 (m),
911 (m), 870 (m), 788 (m), 735 (w), 670 (m), 639 (w), 505 (w), 479
–78 °C. After stirring for two hours bis(diethylamino)pentafluoro-
phenylphosphane (8.00 g; 23.4 mmol) was added dropwise. The
(w), 453 (w) cm–1. MS (EI, 70 eV, pos.): m/z (%) = 368.1 (25) [M]·+, reaction mixture was slowly warmed to room temperature and the
297.0 (14) [C12H16F4NOP]·+, 296.0 (100) [C12H15F4NOP]+, 224.9 (10) solvent evaporated. The raw product was condensed off in dynamic
[C8H6F4OP]+, 196.9 (48) [C6H2F4OP]+. HRMS: calcd. for vacuo at 450 °C. Distillation in dynamic vacuo yielded 8.37 g of the
C16H25F4N2OP·+ 368.16352, found 368.16569.
product (b.p. = 102.4 °C; 20.9 mmol; 89 %) as a yellow oil. H NMR
(CDCl3, r.t.): δ = 1.11 [t, 3J(H,H) = 7 Hz, 12 H, CH3], 3.13 [dq, 3J(P,H) =
10, 3J(H,H) = 7 Hz, 8 H, CH2], 7.42–7.54 (m, 5 H, Ar-C-H) ppm. 13C{1H}
1
p-[(CH3)2N]C6F4P(NEt2)2 (6): A sample of n-butyllithium (12 mL;
3
2
1.6
M in n-hexane, 19.3 mmol) was dissolved in THF (40 mL). The
NMR (CDCl3, r.t.): δ = 15.0 [d, J(P,C) = 3 Hz, CH3], 44.4 [dt, J(P,C) =
19, 5J(F,C) = 1 Hz, CH2], 128.1 (m, C6F4-C), 128.6 (s, C-meta), 129.0
(s, C-para), 130.3 (m, C-ortho) ppm. 13C{19F} NMR (CDCl3, r.t.): δ =
solution was degassed at –80 °C in dynamic vacuo and dimethyl-
amine (19.3 mmol) was condensed onto the solution. After stirring
for 30 min the mixture was warmed to room temperature and
stirred for 10 min. The reaction mixture was cooled to –60 °C and
bis(diethylamino)pentafluorophenylphosphane (6.00 g; 17.5 mmol)
was added dropwise. The reaction mixture was warmed to room
temperature and stirred for 30 min. The solvent was evaporated
and the crude product condensed off in dynamic vacuo at 350 °C.
Distillation in dynamic vacuo yielded 4.52 g of the product (b.p. =
1
3
119.7 (m, C-C6H5), 121.2 [d, J(P,C) = 47 Hz, C-P], 143.8 [d, J(P,C) =
2 Hz, CF], 146.0 [d, 2J(P,C) = 11 Hz, CF] ppm. 19F NMR (CDCl3, r.t.):
δ = –137.2 (m, 2 F, CF-ortho), –144.9 (m, 2 F, CF-meta) ppm. 31P{1H}
NMR (CDCl3, r.t.): δ = 79.5 (m, 1 P, P) ppm. IR (ATR): ν = 3062 (w),
˜
3023 (w), 2967 (w), 2930 (w), 2863 (w), 1603 (w), 1584 (w), 1504 (w),
1459 (m), 1428 (s), 1408 (w), 1375 (m), 1343 (w), 1284 (w), 1198 (m),
1182 (m), 1155 (m), 1097 (w), 1074 (w), 1058 (w), 1014 (s), 961 (s),
927 (m), 914 (m), 841 (w), 778 (m), 748 (w), 723 (m), 694 (m), 670
(m), 647 (m), 635 (w), 615 (w), 498 (w), 457 (w), 415 (w), 403 (w),
379 (w) cm–1. MS (EI, 70 eV, pos.): m/z (%) = 400.2 (20) [M]·+, 329.1
(19) [C16H16F4NP]·+, 328.1 (100) [C16H15F4NP]+, 257.0 (34)
[C12H6F4P]+, 188.0 (26), 161.1 (10) [C7H18N2P]+, 104.1 (16)
[C4H11NP]+. HRMS: calcd. for C20H25F4N2P·+ 400.16860, found
400.16820.
1
90.4 °C; 12.3 mmol; 70 %) as a colorless liquid. H NMR (CDCl3, r.t.):
δ = 1.05 [t, 3J(H,H) = 7 Hz, 12 H, CH3], 2.94 [t, 5J(F,H) = 2 Hz, 6 H,
NCH3], 3.06 [dq, 3J(P,H) = 10, 3J(H,H) = 7 Hz, 8 H, NCH2] ppm. 13C{1H}
3
4
NMR (CDCl3, r.t.): δ = 14.9 [d, J(P,C) = 3 Hz, CH3], 43.4 [td, J(P,C) =
6
2
5
4, J(P,C) = 1 Hz, NCH3], 44.1 [dt, J(P,C) = 19, J(F,C) = 1 Hz, NCH2]
ppm. 13C{19F} NMR (CDCl3, r.t.): δ = 112.8 [d, 1J(P,C) = 44 Hz, C-P],
130.6 (m, C-N), 142.1 [d, 3J(P,C) = 2 Hz, CF], 146.4 [d, 2J(P,C) = 12 Hz,
CF] ppm. 19F NMR (CDCl3, r.t.): δ = –138.8 (m, 2 F, CF-ortho), –151.9
(m, 2 F, CF-meta) ppm. 31P NMR (CDCl3, r.t.): δ = 79.3 (m, 1 P, P)
General Procedure for the Preparation of Phosphinic Acids
ppm. IR (ATR): ν = 2967 (w), 2931 (w), 2863 (w), 2810 (w), 1631 (w),
C6F5P(O)(OH)H (9): A solution of bis(diethylamino)pentafluoro-
phenylphosphane (5.47 g; 16.0 mmol) in diethyl ether (20 mL) was
charged with hydrochloric acid (18 %) at 0 °C and stirred for 1 h.
The phases were separated and the aqueous phase extracted with
diethyl ether (2 × 30 mL). The combined organic phases were dried
˜
1506 (w), 1436 (s), 1374 (m), 1362 (w), 1345 (w), 1292 (w), 1226 (m),
1197 (m), 1097 (w), 1059 (s), 1013 (s), 959 (s), 926 (m), 910 (m), 787
(m), 731 (w), 669 (m), 637 (w), 563 (w), 497 (w), 475 (w), 452 (w),
420 (w), 383 (w) cm–1. MS (ESI, pos.): m/z (%) = 368.3 (100) [M +
Eur. J. Inorg. Chem. 2018, 867–875
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with Mg2SO4 and the solvent was evaporated. Drying in vacuo (19), 308.0 (13), 289.0 (27), 267.0 (100) [M + Na]+, 245.0 (80) [M +
yielded 2.97 g of pentafluorophenylphosphinic acid (12.8 mmol;
80 %) as a colorless powder. 1H NMR (CDCl3, r.t.): δ = 7.82 [d,
1J(P,H) = 635 Hz, 1 H, PH], 12.85 (s, 1 H, POH) ppm. 13C{19F} NMR
H]+. (ESI, neg.): m/z (%) = 242.7 (100) [M – H]–. HRMS: calcd. for
C7H6F4O3P+ 244.99852, found 244.9985.
p-(C2H5O)C6F4P(O)(OH)H (13): (1.89 g; 7.31 mmol; 93 %; colorless
1
2
(CDCl3, r.t.): δ = 106.4 [dd, J(P,C) = 124, J(C,H) = 23 Hz, CP], 137.7
1
3
oil). H NMR (CDCl3, r.t.): δ = 1.44 [t, J(H,H) = 7 Hz, 3 H, CH3], 4.41
[dd, 3J(P,C) = 11, 4J(C,H) = 1 Hz, CF], 144.7 [d, 2J(P,C) = 3 Hz, CF],
3
5
1
[qt, J(H,H) = 7, J(F,H) = 1 Hz, 2 H, OCH2], 7.79 [d, J(P,H) = 627 Hz,
1 H, PH], 12.28 (s, 1 H, POH) ppm. 13C{1H} NMR (CDCl3, r.t.): δ = 15.5
(s, CH3), 71.1 [t, 5J(F,C) = 4 Hz, OCH2] ppm. 13C{19F} NMR (CDCl3, r.t.):
δ = 103.4 [dd, 1J(P,C) = 105, 2J(C,H) = 23 Hz, C-P], 140.5 [dd, 2J(P,C) =
3
4
147.3 [dd, J(P,C) = 1, J(C,H) = 1 Hz, CF] ppm. 19F NMR (CDCl3, r.t.):
δ = –135.3 (m, 2 F, CF-ortho), –144.6 (m, 1 F, CF-para), –158.9 (m, 2
F, CF-meta) ppm. 31P NMR (CDCl3, r.t.): δ = 6.9 [dm, 1J(P,H) = 635 Hz,
1 P] ppm.
3
4
3
12, J(C,H) = 1 Hz, CF], 141.8 [dt, J(P,C) = 2, J(C,H) = 2 Hz, COCH2],
147.4 [t, 5J(C,H) = 1 Hz, CF] ppm. 19F NMR (CDCl3, r.t.): δ = –137.4
(m, 2 F, CF-ortho), –155.7 (m, 2 F, CF-meta) ppm. 31P NMR (CDCl3,
p-(CH3)C6F4P(O)(OH)H (10): (1.78 g; 7.79 mmol; 81 %; colorless
crystals). M.p. 61.4 °C. 1H NMR (CDCl3, r.t.): δ = 2.33 [t, 4J(F,H) = 2 Hz,
3 H, CH3], 7.85 [d, 1J(P,H) = 630 Hz, 1 H, PH], 11.28 (s, 1 H, POH)
ppm. 13C{19F} NMR (CDCl3, r.t.): δ = 8.3 [q, 1J(C,H) = 133 Hz, CH3],
108.8 [dd, 1J(P,C) = 124, 2J(C,H) = 23 Hz, CP], 122.2 [qm, 2J(C,H) =
6 Hz, CCH3], 145.0 (m, CF), 146.4 (s, CF) ppm. 19F NMR (CDCl3, r.t.):
δ = –138.1 (m, 2 F, CF-ortho), –141.4 (m, 2 F, CF-meta) ppm. 31P
NMR (CDCl3, r.t.): δ = 9.5 [dm, 1J(P,H) = 630 Hz, 1 P, P] ppm. IR (ATR):
1
r.t.): δ = 8.2 [d pseudo sept, J(P,H) = 627, J(P,F) = 7 Hz, 1 P, P] ppm.
IR (ATR): ν = 2989 (w), 2939 (w), 2909 (w), 2872 (w), 2413 (w, broad),
˜
2108 (w, broad), 1641 (w), 1499 (w), 1470 (s), 1388 (m), 1366 (w),
1284 (w), 1169 (w), 1103 (s), 955 (s), 878 (m), 835 (m), 761 (m), 731
(w), 663 (w), 606 (w), 576 (w), 509 (m), 451 (m), 439 (m), 386 (m)
cm–1. MS (ESI, neg.): m/z (%) = 514.8 (10) [2M – H]–, 256.8 (100) [M
– H]–. HRMS: calcd. for C8H7F4O3PH+ 259.01417, found 259.01462.
ν = 2934 (w), 2856 (w), 2594 (w, broad), 2427 (w), 2283 (w, broad),
˜
2127 (w, broad), 1650 (w), 1463 (s), 1391 (w), 1379 (w), 1275 (m),
1181 (m), 1125 (m), 1051 (m), 973 (s), 902 (s), 841 (m), 722 (m), 604
(m), 580 (m), 511 (m), 483 (w), 467 (m), 440 (m), 430 (m) cm–1. MS
(ESI, pos.): m/z (%) = 457.0 (100) [2M + H]+, 270.0 (55) [M + H +
ACN]+, 246.0 (13), 228.9 (81) [M + H]+. (ESI, neg.): m/z (%) = 226.7
(100) [M – H]–. HRMS: calcd. for C7H5F4O2PH+ 229.00361, found
229.00430.
p-[(CH3)2N]C6F4P(O)(OH)H (14): (2.08 g, 8.11 mmol, 83 % colorless
1
5
solid). M.p. 106.3 °C. H NMR (CDCl3, r.t.): δ = 3.07 [t, J(F,H) = 3 Hz,
6 H, NCH3], 7.80 [d, 1J(P,H) = 622 Hz, 1 H, PH], 12.43 (s, 1 H, POH)
ppm. 13C{1H} NMR (CDCl3, r.t.): δ = 42.9 [t, 4J(F,C) = 5 Hz, NCH3]
ppm. 13C{19F} NMR (CDCl3, r.t.): δ = 99.4 [dd, J(P,C) = 133, J(C,H) =
23 Hz, C-P], 136.0 (m, C-N), 140.3 [d, 2J(P,C) = 11 Hz, CF], 147.9 (s,
CF) ppm. 19F NMR (CDCl3, r.t.): δ = –138.3 (m, 2 F, CF-ortho), –151.6
(m, 2 F, CF-meta) ppm. 31P NMR (CDCl3, r.t.): δ = 10.2 [d, 1J(P,H) =
1
2
p-(C4H9)C6F4P(O)(OH)H (11): (2.03 g; 7.52 mmol; 92 %; colorless
crystals). M.p. 43.8 °C. 1H NMR (CDCl3, r.t.): δ = 0.94 [t, 3J(H,H) =
7 Hz, 3 H, CH3], 1.37 (m, 2 H, CH2), 1.58 (m, 2 H, CH2), 2.76 [tt,
622 Hz, 1 P, P] ppm. IR (ATR): ν = 2932 (w), 2886 (w), 2853 (w), 2813
˜
(w), 2597 (w, broad), 2398 (w), 2274 (w, broad), 2142 (w, broad),
1634 (w), 1521 (w), 1471 (s), 1435 (m), 1393 (w), 1316 (w), 1303 (w),
1247 (w), 1219 (w), 1175 (m), 1079 (m), 975 (s), 949 (s), 908 (m), 816
(m), 763 (m), 728 (w), 650 (w), 565 (w), 504 (m), 476 (m), 453 (m),
441 (m), 386 (m) cm–1. MS (ESI, pos.): m/z (%) = 537.0 (21), 515.0
(47), 321.1 (14) [M + Na + ACN]+, 299.0 (24) [M + H + ACN]+, 280.0
(27) [M + Na]+, 275.0 (14), 258.0 (100) [M + H]+. (ESI, neg.): m/z (%) =
255.7 (100) [M – H]–. HRMS: calcd. for C8H8NF4O2PH+ 258.03016,
found 258.0300.
4
1
3J(H,H) = 8, J(F,H) = 1 Hz, 2 H, CH2], 7.84 [d, J(P,H) = 627 Hz, 1 H,
PH], 13.00 (s, 1 H, POH) ppm. 13C{1H} NMR (CDCl3, r.t.): δ = 13.8 (s,
CH3), 22.4 (m, CH2), 23.2 (m, CH2), 31.2 (s, CH2) ppm. 13C{19F} NMR
1
2
(CDCl3, r.t.): δ = 108.6 [dd, J(P,C) = 125, J(C,H) = 22 Hz, C-P], 126.8
(m, C-CH2), 144.8 [dt, J(P,C) = 12, 3J(C,H) = 6 Hz, CF], 146.3 (s, CF)
3
ppm. 19F NMR (CDCl3, r.t.): δ = –137.7 (m, 2 F, CF-ortho), –142.7 (m,
2 F, CF-meta) ppm. 31P NMR (CDCl3, r.t.): δ = 8.4 [d pseudo sept,
1J(P,H) = 627, J(P,F) = 7 Hz, 1 P, P] ppm. IR (ATR): ν = 2962 (w), 2934
˜
(w), 2873 (w), 2432 (w, broad), 2278 (w, broad), 2125 (w, broad),
1649 (w), 1464 (s), 1407 (w), 1379 (w), 1333 (w), 1298 (w), 1273 (m),
1251 (w), 1183 (m), 1127 (w), 1105 (w), 1055 (m), 977 (s), 954 (s),
904 (s), 843 (m), 799 (w), 757 (w), 738 (w), 710 (w), 656 (w), 603 (w),
p-[(C2H5)2N]C6F4P(O)(OH)H (15): (2.09 g; 7.32 mmol; 96 %; color-
1
3
less crystals). M.p. 67.2 °C. H NMR (CDCl3, r.t.): δ = 1.14 [t, J(H,H) =
3
5
7 Hz, 6 H, CH3], 3.33 [qt, J(H,H) = 7, J(H,H) = 1 Hz, 4 H, CH2], 7.80
[d, J(P,H) = 624 Hz, 1 H, PH], 9.61 (s, 1 H, POH) ppm. 13C{1H} NMR
1
576 (w), 512 (m), 483 (w), 470 (m), 453 (m), 441 (m), 390 (m) cm–1
.
(CDCl3, r.t.): δ = 13.7 [t, 5J(F,C) = 1 Hz, CH3], 46.8 [t, 4J(F,C) = 4 Hz,
MS (ESI, pos.): m/z (%) = 563.0 (37) [2M + Na]+, 541.0 (24) [2M +
H]+, 470.3 (47), 397.2 (51), 344.2 (19), 334.1 (28) [M + Na + ACN]+,
312.1 (36) [M + H + ACN]+, 293.0 (90) [M + Na]+, 271.1 (100) [M +
H]+. (ESI, neg.): m/z (%) = 268.8 (100) [M – H]–. HRMS: calcd. for
C10H11F4O2PH+ 271.05056, found 271.05140.
NCH2] ppm. 13C{19F} NMR (CDCl3, r.t.): δ = 100.8 [dd, J(P,C) = 130,
1
2J(C,H) = 22 Hz, C-P], 134.3 (s, C-CH2), 141.7 [d, J(P,C) = 11 Hz, CF],
2
147.8 (s, CF) ppm. 19F NMR (CDCl3, r.t.): δ = –138.4 (m, 2 F, CF-ortho),
–149.8 (m, 2 F, CF-meta) ppm. 31P NMR (CDCl3, r.t.): δ = 10.4 [d
1
pseudo sept, J(P,H) = 624, J(P,F) = 7 Hz, 1 P, P] ppm. IR (ATR): ν =
˜
2988 (w), 2965 (w), 2933 (w), 2900 (w), 2875 (w), 2593 (w, broad),
2442 (w), 2407 (w), 2286 (w, broad), 2125 (w, broad), 1988 (w,
broad), 1636 (w), 1519 (w), 1467 (s), 1405 (w), 1381 (w), 1364 (w),
1278 (w), 1191 (m), 1134 (m), 1092 (s), 1019 (m), 972 (s), 953 (s),
915 (s), 884 (m), 808 (w), 793 (w), 776 (w), 758 (w), 725 (w), 650 (w),
567 (w), 506 (m), 470 (m), 434 (m), 420 (m), 406 (m), 395 (m), 380
(m) cm–1. MS (ESI, pos.): m/z (%) = 437.2 (45), 393.4 (94), 381.4 (100),
353.4 (90), 330.1 (20). (ESI, neg.): m/z (%) = 283.8 (100) [M – H]–.
HRMS: calcd. for C10H12F4O2NPH+ 286.06146, found 286.06229.
p-(CH3O)C6F4P(O)(OH)H (12): (11.8 g; 45.4 mmol; 97 %; colorless
crystals). M.p. 60.5 °C. 1H NMR (CDCl3, r.t.): δ = 4.18 [t, 5J(F,H) = 2 Hz,
3 H, OCH3], 7.80 [d, 1J(P,H) = 627 Hz, 1 H, PH], 10.25 (s, 1 H, POH)
ppm. 13C{1H} NMR (CDCl3, r.t.): δ = 62.2 [t, 4J(F,C) = 4 Hz, OCH3]
1
ppm. 13C{19F} NMR (CDCl3, r.t.): δ = 103.5 [d, J(P,C) = 128 Hz, C-P],
2
140.3 [d, J(P,C) = 12 Hz, CF], 142.8 (m, CO), 147.6 (s, CF) ppm. 19F
NMR (CDCl3, r.t.): δ = –137.3 (m, 2 F, CF-ortho), –156.3 (m, 2 F, CF-
1
meta) ppm. 31P NMR (CDCl3, r.t.): δ = 9.1 [dm, J(P,H) = 627 Hz, 1 P,
P] ppm. IR (ATR): ν = 3414 (w, broad), 3025 (w), 2966 (w), 2843 (w),
˜
2790 (w), 2621 (w), 2571 (w), 2509 (w, broad), 2458 (w), 2404 (w, p-(C6H5)C6F4P(O)(OH)H (16): A sample of 8 (3.32 g; 8.30 mmol)
broad), 1692 (m), 1639 (w, shoulder), 1504 (m), 1465 (s), 1431 (m),
1389 (m), 1289 (w), 1190 (m), 1111 (s), 1027 (m, shoulder), 995 (s),
967 (s), 931 (s), 843 (s), 760 (m), 731 (m), 648 (m), 578 (m), 511 (s),
450 (s), 437 (s), 409 (s), 391 (s), 318 (19), 308 (13) cm–1. MS (ESI,
was dissolved in diethyl ether (20 mL) and charged with hydro-
chloric acid (18 %) at 0 °C. The resulting white precipitate was fil-
tered off and washed with diethyl ether (30 mL) and water (3 ×
30 mL). Drying in vacuo yielded 1.94 g of p-(C6H5)C6F4P(O)(OH)H
pos.): m/z (%) = 511.0 (25) [2M + Na]+, 489.0 (16) [2M + H]+, 318.1 (16) (6.68 mmol; 80 %) as a colorless powder. M.p. 285.0 °C. 1H NMR
Eur. J. Inorg. Chem. 2018, 867–875
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1
([D6]DMSO, r.t.): δ = 7.55 (m, 5 H, C6H5), 7.79 [d, J(P,H) = 600 Hz, 1
ACN]+, 331.1 (100), 316.3 (29), 309.1 (18) [M + Na]+, 202.1 (32). (ESI,
neg.): m/z (%) = 284.8 (100) [M – H]–. HRMS: calcd. for C10H10O3F4P–
285.03092, found 285.0314.
H, PH], 8.16 (s, broad, 1 H, POH) ppm. 13C{1H}APT NMR ([D6]DMSO,
r.t.): δ = 126.8 [t, 3J(F,C) = 2 Hz, C], 129.3 (s, CH), 130.2 (s, CH),
130.4 [t, J(F,C) = 2 Hz, CH] ppm. 13C{19F} NMR ([D6]DMSO, r.t.): δ =
4
p-(CH3O)C6F4P(O)(OH)2 (20): (4.14 g; 15.9 mmol; 99 %; colorless
crystals). M.p. 191.6 °C. 1H NMR ([D6]DMSO, r.t.): δ = 4.10 [t, 5J(F,H) =
2 Hz, 3 H, OCH3], 9.61 (s, broad, 2 H, POH) ppm. 13C{1H} NMR
([D6]DMSO, r.t.): δ = 62.4 [t, 5J(F,C) = 4 Hz, OCH3] ppm. 13C{19F} NMR
([D6]DMSO, r.t.): δ = 106.6 [d, 1J(P,C) = 170 Hz, CP], 139.9 (m, COMe),
113.9 [dd, 1J(P,C) = 108, 2J(C,H) = 24 Hz, C-P], 124.0 (m, C-C6H5),
143.6 [d, 2J(P,C) = 10 Hz, CF], 146.3 (s, CF) ppm. 19F NMR ([D6]DMSO,
r.t.): δ = –138.5 (m, 2 F, CF-ortho), –142.8 (m, 2 F, CF-meta) ppm. 31
P
1
NMR ([D6]DMSO, r.t.): δ = –1.0 [dm, J(P,H) = 600 Hz, 1 P, P] ppm. IR
(ATR): ν = 3061 (w), 2644 (w, broad), 2446 (w, broad), 2244 (w,
2
3
140.0 [d, J(P,C) = 14 Hz, CF], 146.3 [d, J(P,C) = 2 Hz, CF] ppm. 19F
NMR ([D6]DMSO, r.t.): δ = –134.5 (m, 2 F, CF-ortho), –157.7 (m, 2 F,
CF-meta) ppm. 31P NMR ([D6]DMSO, r.t.): δ = –1.1 [tt, 3J(P,F) = 7,
˜
broad), 2143 (w, broad), 1643 (w), 1571 (w), 1501 (w), 1471 (s), 1434
(s), 1409 (w), 1387 (w), 1318 (w), 1299 (w), 1233 (w), 1162 (m), 1151
(m), 1023 (w), 986 (s), 959 (s), 921 (m), 865 (m), 809 (w), 781 (m),
749 (w), 726 (m), 693 (m), 659 (w), 643 (w), 613 (w), 518 (m), 475
(w), 461 (m), 414 (w), 382 (m) cm–1. MS (ESI, pos.): m/z (%) = 408.4
(78), 360.4 (100); (ESI, neg.): m/z (%) = 288.8 (100) [M – H]–. HRMS:
calcd. for C12H7O2F4N2PH+ 291.01926, found 291.0197.
4J(P,F) = 2 Hz, 1 P, P] ppm. IR (ATR): ν = 2962 (w), 2841 (w, broad),
˜
2199 (w, broad), 1699 (w), 1643 (w), 1504 (m), 1470 (s), 1438 (m),
1391 (m), 1297 (w), 1186 (m), 1119 (s), 1086 (s), 1027 (s), 964 (s),
928 (s), 717 (m), 669 (m), 584 (m), 552 (s), 479 (m), 430 (m), 421 (m)
cm–1. MS (ESI, pos.): m/z (%) = 339.1 (10), 283.0 (83) [M + Na]+, 261.0
(100) [M + H]+. (ESI, neg.): m/z (%) = 258.8 (100) [M – H]–. HRMS:
calcd. for C7H5F4O4PH+ 260.99344, found 260.9930.
General Procedure for the Preparation of Phosphonic Acids
C6F5P(O)(OH)2 (17): A solution of pentafluorophenylphosphinic
acid (3.50 g; 10.2 mmol) in MTBE (20 mL) was charged with DMSO
p-(C2H5O)C6F4P(O)(OH)2 (21): (1.52 g; 5.58 mmol; 96 %; colorless
(622 mg; 7.96 mmol) and a catalytical amount of iodine (10 mg; crystals). M.p. 112.6 °C. 1H NMR ([D6]DMSO, r.t.): δ = 1.33 [t, 3J(H,H) =
3
0.05 mol-%) at 0 °C and stirred for 24 h. Evaporation of the solvent
and drying in dynamic vacuo yielded 1.88 g of pentafluorophenyl-
phosphonic acid (17) (7.58 mmol; 95 %) as colorless crystals. 1H
NMR ([D6]DMSO, r.t.): δ = 10.26 (s, 2 H, POH) ppm. 13C{19F} NMR
([D6]DMSO, r.t.): δ = 109.5 [d, 1J(P,C) = 166 Hz, CP], 137.5 [d, 3J(P,C) =
7 Hz, 3 H, CH3], 4.36 [qt, J(H,H) = 7, 5J(F,H) = 1 Hz, 2 H, OCH2], 9.81
(s, broad, 2 H, POH) ppm. 13C{1H} NMR ([D6]DMSO, r.t.): δ = 15.3 (s,
CH3), 70.9 [t, 5J(F,C) = 4 Hz, OCH2] ppm. 13C{19F} NMR ([D6]DMSO,
1
3
r.t.): δ = 106.7 [d, J(P,C) = 171 Hz, C-P], 139.0 [q, J(C,H) = 3 Hz, C-
2
3
O], 140.4 [d, J(P,C) = 14 Hz, CF], 146.3 [d, J(P,C) = 2 Hz, CF] ppm.
2
3
14 Hz, CF], 142.6 [d, J(P,C) = 3 Hz, CF], 146.5 [d, J(P,C) = 1 Hz, CF]
19F NMR ([D6]DMSO, r.t.): δ = –134.4 (m, 2 F, CF-ortho), –157.0 (m, 2
ppm. 19F NMR ([D6]DMSO, r.t.): δ = –133.0 (m, 2 F, CF-ortho), –150.5
F, CF-meta) ppm. 31P NMR ([D6]DMSO, r.t.): δ = –1.0 [tt, J(P,F) = 7,
3
(m, 1 F, CF-para), –161.6 (m, 2 F, CF-meta) ppm. 31P NMR ([D6]DMSO, 4J(P,F) = 2 Hz, 1 P, P] ppm. IR (ATR): ν = 3369 (w), 2988 (w), 2939
˜
r.t.): δ = –2.0 (m, 1 P, P) ppm.
(w), 2903 (w), 2773 (w, broad), 2122 (w, broad), 1721 (w), 1644 (w),
1501 (m), 1472 (s), 1388 (m), 1368 (w), 1268 (w), 1202 (w), 1104 (s),
1010 (s), 978 (s), 944 (s), 883 (m), 810 (m), 763 (m), 727 (m), 654 (w),
643 (w), 615 (w), 553 (s), 476 (s), 459 (s), 441 (m), 429 (m), 403 (s)
cm–1. MS (ESI, pos.): m/z (%) = 548.9 (67) [2M + H]+, 372.2 (96), 316.1
(66) [M + H + ACN]+, 275.0 (62) [M + H]+, 251.1 (100), 192.0 (42). (ESI,
neg.): m/z (%) = 272.8 (100) [M – H]–. HRMS: calcd. for C8H7F4O4PH+
275.00909, found 275.0086.
p-(CH3)C6F4P(O)(OH)2 (18): (1.70 g; 6.94 mmol; 89 %; colorless
1
powder). M.p. 193.1 °C (dec). H NMR ([D6]DMSO, r.t.): δ = 2.26 (m,
3 H, CH3), 10.46 (s, broad, 2 H, POH) ppm. 13C{1H} NMR ([D6]DMSO,
r.t.): δ = 7.8 (m, CH3) ppm. 13C{19F} NMR ([D6]DMSO, r.t.): δ = 111.5
[d, 1J(P,C) = 169 Hz, C-P], 119.7 [qm, 2J(C,H) = 6 Hz, C-CH3], 144.9
[dq, 3J(P,C) = 14, 3J(C,H) = 4 Hz, CF], 145.8 [d, 2J(P,C) = 2 Hz, CF]
ppm. 19F NMR ([D6]DMSO, r.t.): δ = –134.8 (m, 2 F, CF-ortho), –143.2
(m, 2 F, CF-meta) ppm. 31P NMR ([D6]DMSO, r.t.): δ = –1.2 [t, 3J(P,F) =
p-[(CH3)2N]C6F4P(O)(OH)2 (22): (2.17 g; 7.94 mmol; 98 %; yellow
1
5
8 Hz, 1 P, P] ppm. IR (ATR): ν = 2754 (w), 2307 (w), 2165 (w), 1689
oil). H NMR ([D6]DMSO, r.t.): δ = 2.95 [t, J(F,H) = 3 Hz, 6 H, NCH3],
˜
(w), 1655 (w), 1463 (s), 1394 (w), 1383 (w), 1277 (m), 1202 (w), 1161
(w), 1130 (w), 1066 (m), 1052 (m), 981 (m), 942 (s), 912 (s), 840 (w),
809 (w), 725 (m), 609 (w), 586 (m), 558 (m), 550 (m), 483 (m), 459
(s), 444 (s) cm–1. MS (ESI, pos.): m/z (%) = 685.5 (31), 554.9 (16),
10.06 (s broad, 2 H, POH) ppm. 13C{1H} NMR ([D6]DMSO, r.t.): δ =
42.7 [t, J(F,C) = 5 Hz, CH3] ppm. 13C{19F} NMR ([D6]DMSO, r.t.): δ =
4
103.1 [d, 1J(P,C) = 176 Hz, C-P], 133.5 (m, C-N), 140.5 [td, 3J(P,F) =
14 Hz, CF], 146.7 [d, 4J(P,F) = 2 Hz, CF] ppm. 19F NMR ([D6]DMSO,
437.2 (100), 379.4 (19), 330.0 (19), 289.0 (28). (ESI, neg.): m/z (%) = r.t.): δ = –135.3 (m, 2 F, CF-ortho), –152.1 (m, 2 F, CF-meta) ppm. 31
P
242.8 (100) [M – H]–. HRMS: calcd. for C7H5F4O3PH+ 244.99852, NMR ([D6]DMSO, r.t.): δ = –0.0 (m, 1 P, P) ppm. IR (ATR): ν = 2925
˜
found 244.9980.
(w), 2893 (w), 2858 (w), 2815 (w), 2676 (w), 2264 (w), 1632 (m), 1521
(w), 1465 (s), 1436 (m), 1398 (w), 1244 (m), 1219 (m), 1075 (m), 1075
(m), 964 (s), 937 (s), 898 (s), 804 (m), 765 (m), 730 (m), 696 (w), 655
(w), 571 (s), 546 (s), 473 (m), 434 (m), 401 (m), 386 (m) cm–1. MS
(ESI, pos.): m/z (%) = 360.4 (100). MS (ESI, neg.): m/z (%) = 271.8
(100) [M – H]–. HRMS: calcd. for C8H8F4O3N2PH+ 274.02507, found
274.0244.
p-(C4H9)C6F4P(O)(OH)2 (19): (630 mg; 2.20 mmol; 98 %; colorless
crystals recrystallized from toluene). M.p. 116.1 °C. 1H NMR
3
([D6]DMSO, r.t.): δ = 0.89 [t, J(H,H) = 7 Hz, 3 H, CH3], 1.31 (m, 2 H,
3
CH2), 1.53 (m, 2 H, CH2), 2.72 [tm, J(H,H) = 7 Hz, 2 H, CH2], 8.96 (s,
2 H, POH) ppm. 13C{1H} NMR ([D6]DMSO, r.t.): δ = 13.5 (s, CH3), 21.7
(s, CH2), 22.3 (m, CH2), 30.6 (s, CH2) ppm. 13C{19F} NMR ([D6]DMSO,
1
r.t.): δ = 111.5 [d, J(P,C) = 168 Hz, C-P], 123.4 (m, C-CH2), 144.4 [dt,
p-[(C2H5)2N]C6F4P(O)(OH)2 (23): (1.85 g; 6.14 mmol; 94 %; colorless
crystals recrystallized from toluene). M.p. 90.4 °C. 1H NMR
([D6]DMSO, r.t.): δ = 1.04 [t, 3J(H,H) = 7 Hz, 6 H, CH3], 3.24 [qm,
3J(P,C) = 13, 3J(C,H) = 5 Hz, CF], 145.4 [d, 2J(P,C) = 2 Hz, CF] ppm.
19F NMR ([D6]DMSO, r.t.): δ = –133.7 (m, 2 F, CF-ortho), –143.9 (m, 2
F, CF-meta) ppm. 31P NMR ([D6]DMSO, r.t.): δ = –0.7 [tm, 3J(P,F) = 3J(H,H) = 7 Hz, 4 H, CH2], 10.34 (s, 2 H, POH) ppm. 13C{1H} NMR
5
8 Hz, 1 P, P] ppm. IR (ATR): ν = 2963 (w), 2935 (w), 2868 (w), 2727
([D6]DMSO, r.t.): δ = 13.2 (s, CH3), 46.2 [t, J(F,C) = 4 Hz, CH2] ppm.
13C{19F} NMR ([D6]DMSO, r.t.): δ = 105.0 [d, 1J(P,C) = 174 Hz, C-P],
131.3 (m, C-N), 142.2 [d, 2J(C,H) = 13 Hz, CF], 146.5 [d, 3J(P,C) = 2 Hz,
CF] ppm. 19F NMR ([D6]DMSO, r.t.): δ = –135.1 (m, 2 F, CF-ortho),
–150.3 (m, 2 F, CF-meta) ppm. 31P NMR ([D6]DMSO, r.t.): δ = –0.3
˜
(w, broad), 2317 (w, broad), 2172 (w, broad), 1694 (w), 1650 (w),
1458 (s), 1407 (w), 1386 (w), 1341 (w), 1329 (w), 1302 (w), 1273 (m),
1248 (w), 1178 (m), 1124 (w), 1099 (w), 1052 (m), 1031 (s), 974 (s),
959 (s), 939 (s), 915 (w), 879 (w), 846 (w), 812 (w), 758 (m), 663 (w),
603 (w), 577 (w), 557 (s), 505 (w), 475 (s), 443 (m), 398 (w) cm–1. MS
[tm, 3J(P,F) = 4 Hz, 1 P, P] ppm. IR (ATR): ν = 2974 (w), 2935 (w),
˜
(ESI, pos.): m/z (%) = 372.1 (47), 360.4 (15), 350.1 (23) [M + Na + 2875 (w), 2612 (w, broad), 2302 (w, broad), 1636 (w), 1462 (s), 1407
Eur. J. Inorg. Chem. 2018, 867–875
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(w), 1379 (w), 1349 (w), 1303 (w), 1275 (m), 1242 (m), 1202 (m),
1179 (m), 1144 (m), 1083 (m), 1006 (m), 968 (s), 930 (s), 841 (m),
801 (m), 759 (m), 735 (m), 695 (w), 656 (w), 587 (m), 560 (s), 517 (s),
501 (m), 493 (m), 465 (s), 446 (m), 434 (m), 391 (s) cm–1. MS (ESI,
pos.): m/z (%) = 437.3 (100), 413.4 (19), 406.2 (69), 393.4 (22), 335.2
(23), 316.3 (12), 302.2 (7) [M + H]+. MS (ESI, neg.): m/z (%) = 327.0
(27), 314.0 (75), 300.0 (100) [M – H]–, 281.3 (16), 255.3 (13). HRMS:
calcd. for C10H12O3F4NPH+ 302.05637, found 302.0563.
p-(C6H5)C6F4P(O)(OH)2 (24): A sample of phosphinic acid 16
(1.94 g; 6.68 mmol) was suspended in toluene (30 mL) and charged
with DMSO (521 mg; 6.68 mmol) and a catalytical amount of iodine
(10 mg; 0.06 mol-%). The resulting suspension was stirred for 24 h.
The product was filtered off and washed with toluene (30 mL) and
MTBE (30 mL). Drying in vacuo yielded 1.60 g of the pure phos-
phonic acid 24 (5.21 mmol; 78 %) as a colorless powder. M.p.
1
165.5 °C. H NMR ([D6]DMSO, r.t.): δ = 7.55 (m, 5 H, C6H5), 9.42 (s, 2
H, POH) ppm. 13C{1H} NMR ([D6]DMSO, r.t.): δ = 126.6 (m, 1 C), 128.8
(s, CH), 129.7 (s, CH), 130.0 (s, CH) ppm. 13C{19F} NMR ([D6]DMSO,
1
r.t.): δ = 113.0 [d, J(P,C) = 168 Hz, C-P], 122.6 (m, C-C6H5), 143.3 [d,
2J(P,C) = 14 Hz, CF], 145.8 [d, 3J(P,C) = 2 Hz, CF] ppm. 19F NMR
([D6]DMSO, r.t.): δ = –133.5 (m, 2 F, CF-ortho), –143.6 (m, 2 F, CF-
3
meta) ppm. 31P NMR ([D6]DMSO, r.t.): δ = –1.5 [t, J(P,F) = 7 Hz, 1 P,
P] ppm. IR (KBr): ν = 3417 (w, broad), 3060 (w), 3020 (w), 2922 (w),
˜
2851 (w), 2720 (w, broad), 2263 (w, broad), 1649 (w), 1572 (w), 1507
(w), 1469 (s), 1436 (s), 1410 (w), 1318 (w), 1300 (w), 1234 (w), 1172
(w), 1114 (w), 1077 (w), 967 (s), 928 (m), 806 (w), 783 (w), 751 (w),
724 (w), 691 (m), 648 (w), 614 (w), 571 (w), 498 (w), 456 (w), 435
(w), 420 (w) cm–1. MS (ESI, pos.): m/z (%) = 685.5 (30), 437.3 (100),
393.2 (29), 316.3 (31). (ESI, neg.): m/z (%) = 304.9 (100) [M – H]–.
HRMS: calcd. for C12H6F4O3P– 304.99962, found 305.0001.
Acknowledgments
This work was supported by Merck KGaA (Darmstadt, Germany).
Solvay (Hannover, Germany) is gratefully acknowledged for do-
nating chemicals. We also acknowledge support by the Deut-
sche Forschungsgemeinschaft (Core Facility GED@BI, Mi477/21-
1). We thank Prof. Dr. Lothar Weber and Dr. Julia Bader for help-
ful discussions.
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Keywords: Phosphonic acid · Phosphinic acid ·
Phosphorus · Fluorine · Phosphanes
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Received: November 30, 2017
Eur. J. Inorg. Chem. 2018, 867–875
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